CN109908970A - A kind of ex situ presulfiding method of hydrogenation catalyst depth vulcanization - Google Patents
A kind of ex situ presulfiding method of hydrogenation catalyst depth vulcanization Download PDFInfo
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- CN109908970A CN109908970A CN201711325661.1A CN201711325661A CN109908970A CN 109908970 A CN109908970 A CN 109908970A CN 201711325661 A CN201711325661 A CN 201711325661A CN 109908970 A CN109908970 A CN 109908970A
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Abstract
The present invention relates to a kind of ex situ presulfiding methods of hydrogenation catalyst depth vulcanization, including (1) to be uniformly mixed vulcanizing agent with oxidized catalyst；(2) it is heat-treated；(3) hydrogen sulfide vulcanizes；(4) appropriate hydrocarbon ils is loaded.Compared with prior art, the method for the present invention has the advantages that (1) compared with routinely carrying sulfur type catalyst, is further reduced the on-stream time of catalyst；(2) the ex situ presulfiding catalyst of depth vulcanization can satisfy hydrogenation plant and go into operation the initial reaction temperature of activation, solves hydrogenator and goes into operation the requirement of operation, improves the safety of hydrogenator；(3) through performance evaluation, the catalyst activity of depth vulcanization is more preferable.
Description
Technical field
The present invention relates to a kind of ex situ presulfiding methods of hydrogenation catalyst, especially go into operation with hydrogenator and operate phase
The ex situ presulfiding technology of coordination.
Background technique
Crude oil in poor quality tendency is increasingly apparent in recent years, and demand of the various countries to clean fuel increasingly increases, and adds hydrogen work
Skill is closed as one of production most effective means of clean fuel with the technology that its efficient hydrogenation catalyst becomes hydrogenation technique
Key.Conventional activity of hydrocatalyst metal is oxidation state, and the substance for really playing active function in actual use is sulphided state,
So need to be vulcanized in reactor before use.Conventional catalyst in-situ presulfurization, but special equipment is needed, increase
Production cost, sulfidation be easy to cause pollution, and required on-stream time is also longer.For this problem, pre- sulphur outside device in recent years
Change technology is come into being, the EPRES developed such as Fushun Petrochemical Research Institute®Ex situ presulfiding technology.Pre- sulphur outside typical device
Change technology is to load to sulphur-containing substance and auxiliary agent in oxidized catalyst, these ex situ presulfiding catalyst for carrying sulfur type are adding
Hydrogen production device go into operation activation initial reaction temperature it is lower, need to boost to certain pressure at a lower temperature and activated, it is no
Then activation effect is undesirable, and itself operation of this and hydrogenator has larger contradiction.
Hydrogenator is the main device of hydrogenation plant, and safe handling plays a significant role, hot wall hydrogenation reaction
The common stainless steel material of device has hydrogen embrittlement characteristic, and (toughness under low temperature dissolved with hydrogen Steel material is greatly lowered, and brittleness is significantly
Increase), after reactor comes into operation, the temper embrittlement of material is inevitable.Therefore, hot-wall hydrogenation reactor shutting down process
In, when Wall Temperature is lower, the toughness of wall material be possible to due to hydrogen embrittlement and Temper brittleness collective effect and significantly under
Drop.In order to avoid accident generation, the measure being usually taken is the minimum pressurization temperature for setting reactor, usual minimum pressurization temperature
It is set as 125 ~ 145 DEG C.In the use process of hot-wall hydrogenation reactor, Material degradation situation can be with the growth of active time
And gradually increase, this make reactor come into operation initial stage be partial to safety pressure limiting temperature-boosting measure arrived reactor military service later period just
It may become dangerous.Therefore, the safe condition that uses of reactor is accurately inferred according to the Material degradation situation of reactor, and
It determines reasonable minimum pressurization temperature, is highly important for the safety for ensureing that hot-wall hydrogenation reactor is used for a long time.
Therefore, the operation that goes into operation of the activation act of ex situ presulfiding catalyst and hydrogenator, which exists, mismatches place.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of ex situ presulfiding processing method of hydrogenation catalyst, can be with
Effectively solves the problems, such as hydrogenating catalyst outside presulfurization go into operation with hydrogenator operate it is unmatched.
The ex situ presulfiding method of hydrogenation catalyst of the invention, including following content:
(1) vulcanizing agent is uniformly mixed with oxidation state hydrogenation catalyst；
(2) mixture of step (1) is heat-treated；
(3) intermediate material after step (2) heat treatment is further supplemented into presulfurization, hydrogen sulfide using the material containing hydrogen sulfide
Supplement presulfurization condition are as follows: temperature be 50 ~ 350 DEG C, preferably 90 ~ 250 DEG C, the processing time be 10 ~ 240min, preferably 30 ~
60min；
(4) intermediate material for vulcanizing step (3) hydrogen sulfide loads appropriate hydrocarbon ils, obtains the pre-sulfide catalyst of depth vulcanization.
In the method for the present invention, hydrogenation catalyst gasoline described in step (1), kerosene, diesel oil and wax oil hydrogenation purification add hydrogen
Cracking, is hydrocracked prerefining, and wax hydrofining reforms prerefining, the catalyst of multiple types such as residual hydrogenation.Such catalyst
Be active component with one or more of W, Mo, Ni, Co generally using aluminium oxide as carrier, in catalyst can containing Si, P,
B, one or more of auxiliary agents such as Ti, Zr.
In the method for the present invention, vulcanizing agent described in step (1) can be the sulphur-containing substance of this field routine, can be simple substance
Sulphur and/or sulfur-containing compound.It can be single substance, be also possible to mixture, preferably cheap elemental sulfur (i.e. sulphur).Specifically
Such as carbon disulfide, dimethyl disulfide, tert-butyl polysulfide, the more sulphur of tertiary nonyl, thiocarbamide, butyl mercaptan, ethanethio, sulphur
Powder, SZ-54(commodity), polysulfide, vulcanization ammonia, mercaptan, thiophenol, thioether, one of sulfolane and dimethyl sulfoxide etc. or several
Kind.The dosage of vulcanizing agent, which is generally catalyst theory, needs the 50% ~ 110% of sulfur content, preferably 65% ~ 100%, most preferably 80% ~ 95%.It urges
Agent theory needs sulfur content to be fully converted to sulfide (Co for institute's metallic components on catalyst9S8、MoS2、Ni3S2、WS2) when need
Want the amount of sulphur.In order to which vulcanizing agent is uniformly mixed with oxidation state hydrogenation catalyst, other appropriate vulcanization aids, such as ability can be added
There are commonly solvents etc. in domain.Vulcanization aid can be one or more of hydrocarbon ils, organic carboxylic ester, and hydrocarbon ils is generally various
One or more of kerosene, diesel oil, lam-oil, white oil, lube base oil, straight run and heavy distillate of decompression etc., it is best
It is the hydrocarbon ils that secondary operation obtains, such as the above-mentioned hydrocarbon ils that catalytic cracking, thermal cracking technique obtain.Organic carboxylic ester, which can be, to be contained
There are the organic carboxyl acid esters of 6 ~ 60 carbon atoms, preferred fat acid glyceride.The dosage of vulcanization aid is catalyst weight
0.1% ~ 30%, preferably 1% ~ 15%, more preferable 2% ~ 10%.
In the method for the present invention, the temperature of heat treatment described in step (2) is generally 70 ~ 300 DEG C, preferably 90 ~ 230 DEG C of conditions
Under, heat treatment time is generally 10 ~ 480min, preferably 15 ~ 240min.
The method of the present invention (1), (2) can complete step by step, can also synchronously complete.
In the method for the present invention, step (3) can be containing for the discharges such as Petrochemical Enterprises hydrogenation plant containing the material of hydrogen sulfide
Have and is vented outside the material of hydrogen sulfide, such as low point of gas of hydrogenation plant, hydrogenation plant recycle hydrogen.Hydrogen sulfide introduces prevulcanisation-devices
Amount, which is generally catalyst theory, needs the 3% ~ 30% of sulfur content, preferably 5% ~ 20%, most preferably 8% ~ 15%.Vulcanizing agent and hydrogen sulfide always draw
Entering amount and being generally not less than catalyst theory needs the 90% of sulfur content.
In the method for the present invention (4), hydrocarbon ils load capacity is the 0.5% ~ 20%, preferably 2.0% ~ 10% of catalyst weight,
Hydrocarbon ils is generally the hydrocarbon ils of petroleum refining process acquisition, generally requires initial boiling point at 150 DEG C or more, and preferably 180 DEG C or more.
It, after step (4) or with step (4) simultaneously, can be according to the need of adjustment catalyst property in the method for the present invention
It wants, introduces the modifying agent such as the substances such as organic acid, organic nitrogen.Modifying agent load capacity is the 0.5% ~ 20% of catalyst weight, preferably
It is 2.0% ~ 10%.It can be using suitable drying and processing after step (4).
When carrying out ex situ presulfiding to hydrogenation catalyst using the method for the present invention, (1) and conventional load advantage is achieved that
Sulfur type catalyst is compared, and the on-stream time of catalyst is further reduced；(2) the ex situ presulfiding catalyst of depth vulcanization can expire
Sufficient hydrogenation plant goes into operation the initial reaction temperature of activation, solves hydrogenator and goes into operation the requirement of operation, improves plus hydrogen is anti-
Answer the safety of device；(3) through performance evaluation, the catalyst activity of depth vulcanization is more preferable.
Specific embodiment
Select existing hydrogenation catalyst to carry out ex situ presulfiding processing below, further illustrate the method for the present invention process and
Effect, but do not limit the scope of the invention, main material property involved in embodiment is as follows.
1 this field common diesel hydrogenation catalyst of table
The main character of the industrial soya-bean oil of table 2
The main character of 3 light oil of table
4 kerosene main character of table
The main character of 5 diesel oil of table
Embodiment 1
Ex situ presulfiding is carried out to the FHUDS-5 catalyst of the diesel oil hydrogenation in table 1.
(1) by vulcanizing agent (elemental sulfur, dosage are that the theory of diesel oil hydrogenation catalyst needs the 90% of sulfur content), vulcanization aid (work
The mixture of industry soya-bean oil and kerosene weight ratio 1:1, dosage are the 5% of diesel oil hydrogenation catalyst FHUDS-5 weight) it is uniformly mixed, it obtains
To presulfurization raw material；Presulfurization raw material is uniformly mixed with diesel oil hydrogenation catalyst；
(2) mixed material of step (1) is heat-treated 1 hour under the conditions of 140 DEG C.
(3) by the intermediate material of step (2) use low point of gas of hydrogenation plant handled (hydrogen sulfide volume content for
12%), hydrogen sulfide reference amount is that the theory of diesel oil hydrogenation catalyst needs the 15% of sulfur content, processing pressure 3.0MPa, in 320 DEG C of conditions
Lower processing 1 hour.
(4) intermediate material of step (3) loads straight-run diesel oil, and load capacity is catalyst diesel oil hydrogenation catalyst FHUDS-5
The 3% of weight obtains the pre-sulfide catalyst 1 of depth vulcanization.
Comparative example 1
As described in Example 1, cancellation step (2), step (1) elemental sulfur introduction volume are that the theory of diesel oil hydrogenation catalyst needs sulphur
The 105% of amount obtains preloading sulfur diesel and adds hydrogen FHUDS-5 catalyst A.
Embodiment 2
Ex situ presulfiding is carried out to the FHFHUDS-5 in table 1.
(1) by vulcanizing agent (elemental sulfur, dosage are that the theory of diesel oil hydrogenation catalyst needs the 115% of sulfur content), vulcanization aid
(mixture of industrial soya-bean oil and gasoline weight ratio 2:1, dosage are the 9% of diesel oil hydrogenation catalyst FHFHUDS-5 weight) mixing is equal
It is even, obtain presulfurization raw material；Presulfurization raw material is uniformly mixed with diesel oil hydrogenation catalyst；
(2) mixed material of step (1) is heat-treated 0.5 hour under the conditions of 150 DEG C.
(3) material that step (2) obtain is handled into (hydrogen sulfide volume content using exhaust outside hydrogenation plant recycle hydrogen
For 6%), hydrogen sulfide reference amount is that the theory of diesel oil hydrogenation catalyst needs the 5% of sulfur content, pressure 0.6MPa, hot under the conditions of 180 DEG C
Processing 1 hour.
(4) citric acid and lubricating oil are loaded in the material that step (3) obtains, contains citric acid 5% by catalyst weight
Material is introduced with containing lubricating oil 7%, is then handled 2 hours at 120 DEG C, the pre-sulfide catalyst 2 of depth vulcanization is obtained.
Comparative example 2
As described in Example 2, cancellation step (3), step (1) elemental sulfur introduction volume are that the theory of diesel oil hydrogenation catalyst needs sulphur
The 120% of amount obtains preloading sulfur diesel and adds hydrogen FHUDS-5 catalyst B.Cancellation step (4), step (1) elemental sulfur introduction volume are bavin
The theory of oil hydrogenation catalysts needs the 120% of sulfur content, obtains preloading sulfur diesel and adds hydrogen FHUDS-5 catalyst C.Cancellation step (3) and
(4), step (1) elemental sulfur introduction volume is that the theory of diesel oil hydrogenation catalyst needs the 120% of sulfur content, obtains preloading sulfur diesel and adds hydrogen
FHUDS-5 catalyst D.
Embodiment 3
The catalyst that the ex situ presulfiding catalyst that Examples 1 to 2 obtains depth vulcanization is obtained with comparative example 1~2 is commented
Valence test.(initial activation temperature is in presence of hydrogen for the initial activation temperature of main contrast's difference ex situ presulfiding catalyst
Obvious release water outlet is standard, the minimum pressurization temperature of corresponding hydrogenator), and the relative activity after activation.
Initial activation temperature testing method are as follows: after 90 DEG C of nitrogen are 5 hours dry, in 0.2MPa(gauge pressure) and hydrogen presence
Under, it gradually heats up, the temperature that device outlet material is obviously collected into water is initial activation temperature.
Activation process condition are as follows: at 320 DEG C, in 6MPa(gauge pressure) and in the presence of hydrogen, activate 15 hours.
Relative activity evaluation condition are as follows: using mixed diesel as feedstock oil (table 6), reaction pressure 6.0MPa, hydrogen oil volume
Than for 350:1, volume space velocity 2.5h-1, reaction temperature be 350 DEG C.On the basis of the activity of catalyst D (100).
6 raw material main character of table
The initial activation temperature (minimum pressurization temperature) of 7 catalyst of table compares
The hydrogenation activity of 8 catalyst of table compares
| Catalyst number | 1 | 2 | A | B | C | D |
| Desulfurization degree, % | 142 | 150 | 124 | 120 | 103 | 100 |
As can be seen from the above results, the ex situ presulfiding catalyst that the method for the present invention obtains has higher initial activation temperature
(being conducive to match with the operating condition of hydrogenator) and higher catalytic performance.
Claims (10)
1. a kind of ex situ presulfiding method of hydrogenation catalyst, including following content:
(1) vulcanizing agent is uniformly mixed with oxidation state hydrogenation catalyst；
(2) mixture of step (1) is heat-treated；
(3) intermediate material after step (2) heat treatment is further supplemented into presulfurization, hydrogen sulfide using the material containing hydrogen sulfide
Supplement presulfurization condition are as follows: temperature be 50 ~ 350 DEG C, preferably 90 ~ 250 DEG C, the processing time be 10 ~ 240min, preferably 30 ~
60min；
(4) intermediate material for vulcanizing step (3) hydrogen sulfide loads appropriate hydrocarbon ils, obtains the pre-sulfide catalyst of depth vulcanization.
2. according to the method for claim 1, it is characterised in that: vulcanizing agent described in step (1) is elemental sulfur and/or sulfur-bearing
Compound, the dosage of vulcanizing agent are that catalyst theory needs the 50% ~ 110% of sulfur content, preferably 65% ~ 100%, most preferably 80% ~ 95%.
3. according to the method for claim 1, it is characterised in that: vulcanization aid is added in step (1), vulcanization aid is organic
Solvent, the dosage of vulcanization aid are the 0.1% ~ 30% of catalyst weight, preferably 1% ~ 15%, more preferable 2% ~ 10%.
4. according to the method for claim 1, it is characterised in that: the temperature of heat treatment described in step (2) is 70 ~ 300 DEG C,
It is preferred that heat treatment time is 10 ~ 480min, preferably 15 ~ 240min under the conditions of 90 ~ 230 DEG C.
5. according to the method for claim 1, it is characterised in that: step (1), (2) substep are completed, or synchronously completed.
6. according to the method for claim 1, it is characterised in that: the amount that step (3) hydrogen sulfide introduces prevulcanisation-devices is to urge
Agent theory needs the 3% ~ 30% of sulfur content, preferably 5% ~ 20%, most preferably 8% ~ 15%.
7. according to the method for claim 1, it is characterised in that: hydrocarbon ils load capacity is catalyst weight in step (4)
0.5% ~ 20%, preferably 2.0% ~ 10%.
8. according to the method for claim 7, it is characterised in that: the hydrocarbon ils is the hydrocarbon ils that petroleum refining process obtains,
The initial boiling point of hydrocarbon ils is at 150 DEG C or more, and preferably 180 DEG C or more.
9. according to method described in claim 1 or 7, it is characterised in that: after step (4) or with step (4) simultaneously, introduce
Organic acid, organic nitrogen modifying agent；Drying and processing is used after step (4).
10. according to the method for claim 9, it is characterised in that: modifying agent load capacity be catalyst weight 0.5% ~
20%, preferably 2.0% ~ 10%.
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| CN103100444A (en) * | 2011-11-09 | 2013-05-15 | 中国石油化工股份有限公司 | Preparation method of prevulcanization type catalyst |
| CN107456974A (en) * | 2016-06-03 | 2017-12-12 | 中国石油化工股份有限公司 | A kind of hydrogenation catalyst and its preprocess method methods and applications desulphurizing activated with hydrogenation catalyst is improved |
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2017
- 2017-12-13 CN CN201711325661.1A patent/CN109908970A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1516667A1 (en) * | 2003-09-19 | 2005-03-23 | Institut Français du Pétrole | Hydrorefining and/or hydroconversion catalyst comprising an active phase in the form of a solid solution sulfide of molybdenum and tungsten |
| CN101492607A (en) * | 2008-01-23 | 2009-07-29 | 中国石油化工股份有限公司 | Hydrogenation catalysts precuring method and start working method of hydrogenation process |
| WO2011075463A2 (en) * | 2009-12-18 | 2011-06-23 | Exxonmobil Research And Engineering Company | Hydroprocessing catalysts and their production |
| CN102443427A (en) * | 2010-10-13 | 2012-05-09 | 中国石油化工股份有限公司 | Start-up vulcanizing method of hydrocracking process |
| CN103100444A (en) * | 2011-11-09 | 2013-05-15 | 中国石油化工股份有限公司 | Preparation method of prevulcanization type catalyst |
| CN107456974A (en) * | 2016-06-03 | 2017-12-12 | 中国石油化工股份有限公司 | A kind of hydrogenation catalyst and its preprocess method methods and applications desulphurizing activated with hydrogenation catalyst is improved |
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